Liquid detergent composition



United States Patent 3,232,880 LIQUID DETERGENT COMPOSITION Marvin L. Mausner, Teaneck, John S. Smith, West Paterson, and Joseph Castellano, Garfield, N.J., assignors to Ultra Chemical Works, Inc, Paterson, N.J., a corporation of Delaware N0 Drawing. Filed Apr. 10, 1961, Ser. No. 101,660

4 Claims. (Cl. 252-137) This invention is directed to new and useful heavy duty liquid detergent compositions.

The production and marketing of heavy duty liquid detergent compositions has been known for a number of years and various formulations have been evolved. In general, such compositions contain synthetic organic nonsoap water-soluble anionic detergents in combination with other ingredients, notably higher fatty acid alkanol amides, sodium tripolyphosph-ate, tetrasodium or tetrapotassium pyrophosphate, sodium carboxymethyl cellulose, sodium toluene sulfonate, sodium silicates, alkalies such as sodium carbonate, and the like, the solids content being about to by weight, balance water. Such heavy duty liquid detergent compositions are designed to remove difiicultly removable soil from fabrics and to prevent redeposition of the soil on the Washed fabrics. They are disclosed in various United States patents, illustrative of which are Nos. 2,859,182; 2,860,107; 2 ,864,770; 2,877,185; 2,877,186; 2,914,482; 2,920,045; 2,927,081 and 2,954,348.

One of the problems in the production of fully satisfactory heavy duty liquid detergent compositions is to provide compositions which have high solids content, say to which are stable and from which separation of ingredients or formations of layers will not occur on standing over appreciable periods of time, and which do not require the presence of silicates and which, therefore, are mild so far as their lack of irritation to the skin is conce'rned. The production of such compositions requires not only a careful balancing of a number of essential ingredients but, in addition, it also requires particular mixing or blending procedures which, unless reasonably followed, will not result in the production of a satisfactory final heavy duty liquid detergent composition.

The practice of the present invention, hereafter described in detail, results in the production of excellent heavy duty liquid detergents, in which the solids content can be up to 60% or even higher, which remain stable over prolonged periods of time over a wide temperature range, which are quite mild in their reaction to the skin, and which possess highly desirable soil removal characteristics.

The heavy duty liquid detergents of the present in vention contain, as essential ingredients, in the ranges of proportions set forth hereafter, (1) water-soluble lower alkanolamine salts of higher alkyl benzene or toluene sulfonic acids, (2) an organic solubilizing agent or mixture of solubilizing agents, (3) certain polyphosphates, notably tetrasodium or tetrapotassium pyrophosphate, or mixtures of sodium tripolyphosphate with sodium hexametaphosphate, (4) certain fatty acid alkanolamides, (5) sodium carboxymethyl cellulose, and (6) methylcellulose. Supplemental agents of various types, referred to here after, are desirably included in the heavy duty liquid detergents but they are not essential.

It is important to the accomplishment of the objects of the present invention to utilize, as an essential detergent material, in combination with the other lIllgl dients, a water-soluble alkanolamine salt of an alkyl benzene or toluene sulfonic acid in which the alkyl group contains predominately from 8 to 16 carbon atoms and more particularly predominately 12 to 15 carbon atoms, especially satisfactory being the alkanolamine salts of dodecyl benzene sulfonic acid and tridecyl benzene sulfonic acid and mixtures thereof. The lower alkanolamines which are utilized to form the salts of said alkyl benzene sul-fonic acids may be selected from. a wide group including, by way of example, diethanolamine, triethanolamine, di-isopropanolamine, tri-isopropanolamine, di-ethylethanolamine, butanolamine, isobutanolamine, glycerolan'iines, hydroxyethyl ethylenediamine, and the like. The alkanolamines utilized should, for best results, have a vapor pressure not appreciably below that of diethanolamine, and they should form, with the alkyl benzene or toluene sulfonic acids, salts which are highly soluble in water. Diethanolarnine and triethanolamine and commercial mixtures containing the same are especially satisfactory. The alkyl benzene sulfonic acids are best made by alkylating benzene or toluene with polypropylenes but other sources of the alkyl radicals can, of

course, be utilized. Patents Nos. 2,477,382 and 2,477,383

the ingredients to produce the final liquid detergent prod- The alkanolamine salts of the alkyl benzene or not. toluene sulfon-ic acids should constitute between 10 and 25% by weight of the heavy duty liquid detergent com,. position and, more desirably, should lie within the range of 16 to 21%. It may be noted that alkanolamine salts of allyl benzene sulfonic acids have heretofore been utilized in liquid detergents, but, so far as known, they have not been successfully employed in heavy duty liquid detergent compositions.

The organic solubilizing agents which are utilized in; the practice of the invention have heretofore, generally,

speaking, been utilized in heretofore knownheavy duty liquid detergent compositions as shown, for instance,qin

various of the patents cited above, particularly Nos 2,859,182 and 2,877,185. They are exemplified by so-:

dium or potassium salts of aryl sulfonic acids such as benzene sulfonic acid, toluene sulfonic acid, ethyl benzene sulfonic acid, xylene sulfonic acids which includes mixed isomers, isopro-pyl benzene sulfonic acid; lower alkyl ethers of glycols and polyglycols such as monobutyl ether of ethylene glycol, monobutyl ether of diethylene glycol, monoisopropyl ether of diethylene glycol, monoethyl ether o-f butylene glycol; and mixtures of any of the foregoing with such glycols as hexylene glycol, heptylene glycol, and the like. Th proportions of the solubilizers will generally range from about 5 to 12% on the active basis,

by Weight of the heavy duty liquid detergent composition, with a particularly preferred range being from 6 to 9%.; The polyphosphates, which serve to impartlthe heavy duty detergent characteristics, are, generallyselected from the group comprising tetrapotassium pyrophosphate and 1 Other polyphosphates pentapotassium tripolyphosph-ate. which can be used, but less desirably, are mixtures of sodium tripolyphosphate with suflicient sodium hexarmetaphosphate, preferably inabout a 1:1 ratio in the mixture, to effect proper solubilization of the sodium tripolyphosphate in the heavy duty liquid detergent. compositions. The polyphosphate content will generally range from about 15 to 22% by weight of the heavy duty liquid detergent composition with 18 to 20% representing a preferred range. I

The next essential ingredient is a fatty acid alkanolamide and it may be either a monoalkanolamide or a dialkanolamide. Particularly satisfactory are those alkanolamides of predominately lauric or myristic (C and C acids or G -C unsaturated fatty acids such as oleic" t acid. While the aforesaid higher fatty acid alkanolamides of various alkanolamines can be used such as those derived from monoethanolamine, diethanolamine, monoand di-propanolamines, monoisopropanolamine, diisopropanolarnine, butanolamines, hydroxyethyl ethylene diamine, glycerol monoamines, and the like, especially useful are the lauric, myristic and coconut oil mixed fatty acid (or special fractions thereof high in lauric acid) alkanolamides of monoethanolamine, diethanolamine and monoisopropanolamine. Monoalkanolamides are ferred due to stability characteristics. The proportions of said alkanolamides generally will range from 2 to 6%, with 3 to 4% being particularly preferred, said percentages being by weight of the heavy duty liquid detergent compositions.

The remaining essential ingredients, which have heretofore been used in heavy duty liquid detergent formulations, are sodium carboxymethyl cellulose and methylcellulose. The carboxymethyl cellulose serves as a soil suspending agent and the methylcellulose also functions at least in part for the same purpose but, in addition, it aids in maintaining the carboxymethyl cellulose in stable suspension in the heavy duty liquid detergent compositions. Illustrative forms of these ingredients which can be utilized in the compositions of the present invention are those disclosed in U.S. Patent No. 2,860,107, namely, sodium carboxymethyl cellulose containing about 0.7 mol of carboxymethyl groups per anhydroglucose unit; and methylcelluose (Methocel) of about 25 centipoise viscosity in a 2% aqueous dispersion having 27.532% methoxyl groups per cellulose molecule. It has been found, however, to be especially advantageous to use, in the compositions of the present invention, a sodium carboxymethyl cellulose in which there are about 1.25 mols of carboxymethyl groups per anhydroglucose unit. The sodium carboxymethyl cellulose is used generally in proportions of about 0.1 to 0.3%, preferably 0.15 to 0.2%; and the methylcellulose is used generally in proportions of about 0.5 to 0.8%, preferably 0.6 to 0.7%, based on the weight of the heavy duty liquid detergent compositions.

As stated above, various supplemental ingredients, optional butdesirable, can be incorporated into the heavy duty liquid detergent compositions. These comprise, by way of example, various ethylene oxide adducts which can be employed in small proportions. They are derived from reacting ethylene oxide with an alkyl phenol or a higher molecular weight aliphatic alcohol such as octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol or tetradecyl alcohol, or mixtures of said alcohols whereby to introduce from 3 to 15 oxyethylene groups into the molecule. The alkyl radical of the alkyl phenol may contain from to carbon atoms but especially satisfactory is nonyl'phenol; and use of adducts thereof containing a chain of from 4 to 6 ethylene oxide groups is preferred. The ethylene oxide adducts, when utilized, are employed in proportions in the range of 0.5 to 4%, generally from 1 to 2%, said percentages being by weight of the heavy duty liquid detergent compositions. Other supplemental ingredients are chelating agents such as tetrasodium salt of ethylenediamine tetra-acetic acid, fluorescent dyes, optical brighteners, perfumes, bacteriostats, coloring dyes, corrosion inhibitors, and the like, all of which, when utilized, are employed in small proportions, most of them well below 1% by weight of the heavy duty liquid detergent compositions.

The balance of the essential ingredients is water, in which the other ingredients are dissolved or suspended, and which, in the particularly preferred aspects of the invention, will be present in proportions of 40 to by weight of the heavy duty liquid detergent compositions.

The following examples are illustrative of particularly preferred embodiments of the invention which are not to be construed as in any way limitative of the invention since numerous other embodiments can readily be evolved pre- d in the light of the guiding principles and teachings provided herein.

Example I Weight percent Diethanolamine salt of dodecyl benzene sulfonic acid 20.86 Sodium xylene (mixed isomers) sulfonate (40% active) 18.75 Hexylene glycol 2.0 4 mol ethylene oxide adduct of nonyl phenol 1.0 Laurie acid amide of mono-isopropanolamine 3.0 Tetrapotassium pyrophosphate 19.0

Tetrasodium salt of ethylene diamine tetra-acetic acid 3.0 Carboxymethyl cellulose (DuPont P-M) 0.15 Methocel 0.7 Sodium dichromate 0.1 Tinopal RES 200% 0.05 Tinopal 4BM 0.05 Perfumes and color (to suit).

Water (additional) 31.1

The composition of Example 1 was prepared as follows, all parts stated being by weight:

A. 0.825 parts of sodium carboxymethyl cellulose Were dissolved in 82.5 parts water at 80-85 degrees C. to provide a substantially uniform solution free of gelatinous masses. Then 3.85 parts of the Methocel were added with.

stirring, while maintaining a temperature of 80-85 degrees C., and vigorous mixing was carried out for about 10 minutes after the addition of the Methocel was completed. The mixture was cooled to 60 degrees C. and 70.2 parts of cold water (15 degrees C. or below) were added and mixing Was carried out for about /2 hour or until an essentially uniform mixture was obtained. Then 55 parts of sodium xylene (mixed isomers) sulfonate (high ratio, drum dried), 76 parts of dodecyl benzene sulfonic acid, and 6 parts of tetrasodium salt of ethylenediamine tetra-acetic acid were added and mixed and circulated to obtain as uniform a mixture as was reasonably possible.

B. To 16.5 parts of molten lauric acid amide of monoisopropanolamine, 11 parts of hexylene glycol and 5.5 parts of 4-mol ethylene oxide adduct of nonyl phenol were added, heated to 60 degrees C. and 0.27 parts of Tinopal RES 200 were dissolved therein. Then 0.27 parts of Tinopal 4BM were added and dispersed by vigorous agitation.

C. The compositions of parts A and B hereof were then thoroughly mixed together and parts of a 60% aqueous solution of tetrapotassium pyrophosphate were added slowly with a minimum of air entrainment and maximum agitation at a temperature of about 50 degrees C., followed by the addition of 38.4 parts of diethanolamine, and the perfume was then added. In order to provide the most effective stability to the finished heavy duty liquid detergent, it is important that the addition of the diethanolamine, or other alkanolamine, be effected after the addition of the tetrapotassium pyrophosphate or other polyphosphates.

D. To 7.65 parts of water at 60 degrees C., 0.2 parts of dye (e.g. Calcocid Blue EGAmerican Cyanamid Company) were added and then 0.55 parts sodium dichromate dihydrate were added. The resulting mixturewas then added to the composition produced in part C hereof. The final heavy duty liquid detergent composition contained approximately 58% of solids.

As stated previously, the stability of the final heavy duty liquid detergent depends to a material extent upon the order of certain of the above-disclosed mixing steps and temperatures, especially in part C where the diethanolamine follows the addition of the tetrapotassium pyrophosphate, and where the temperature is approximately 50 degrees C. It is especially advantageous to use a temperature of about 50 degrees C. or a temperature in Example 2 Weight percent Diethanolamine salt of dodecyl benzene sulfonic acid 20.86 Sodium xylene (mixed isomers) sulfonate (40% active) 20 6-mol ethylene oxide adduct of nonyl phenol 1.5 Laurie acid amide of monoethanolamine 3.0 Tetrapotassium pyrophosphate 20 Carboxymethyl cellulose (DuPont P-125M) 0.15 Methocel (Dow cps.) 0.7 Perfumes and color (to suit). Water (additional) 32 Example 3 Weight percent Diethanolamine salt of dodecyl benzene sulfonic caba a 8111i125115552551 8;i is fiii: 0.1's

Methocel (Dow cps.) 0.7 Perfumes and color (to suit). Water (additional) 31.1

The compositions of Examples 2 and 3 are made in the manner described in Example 1.

What we claim as new and desire to protect by Letters Patent of the United States is:

1. In a method of making a heavy duty liquid detergent of the following composition in approximately the stated percentages by weight:

Member selected from the group consisting of water-soluble lower alkanolamine salts of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains predominately from 8 to 18 carbon atoms Organic solubilizing agent selected from the group consisting of lower alkyl benzene sulfonates and lower alkyl ethers of glycols and and polyglycols Fatty acid alkanolamide in which the fatty acid radical is selected from group consisting of those derived from fatty acids containing predominately from 12 to 14 carbon atoms and the C to C unsaturated fatty acids A member selected from the group consisting of sodium and potassium polyphosphates to 22 Sodium carboxymethyl cellulose 0.1 to 0.3

Methyl cellulose 0.5 to 0.8

Water 40 to 50 the steps which comprise forming a substantially uniform solution in water of the sodium carboxymethyl cellulose, methyl cellulose, the organic solubilizing agent and the member selected from the group consisting of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains predominately from 8 to 18 carbon atoms, then adding the fatty acid alkanolamide in molten form and thoroughly admixing, then adding an aqueous solution of the polyphosphate, and then adding the lower alkanolamine in amounts essentially to form the alkanolamine salt of said member selected from the group consisting of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains from 8 to 18 carbon atoms.

2. In a method of making a heavy duty liquid detergent of the following composition in approximately the stated percentages by weight:

Member selected from the group consisting of water-soluble lower alkanolamine salts of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains predominately from 8 to 18 carbon atoms 10 to 25 Organic solubilizing agent selected from the group consisting of lower alkyl benzene sulfonates and lower alkyl ethers of glycols and polyglycols 5 to 15 Fatty acid alkanolamide in which the fatty acid radical is selected from group consisting of those derived from fatty acids containing predominately from 12 to 14 carbon atoms and the C to C unsaturated fatty acids 2 to 6 A member selected. from the group consisting of sodium and potassium polyphosphates 15 to 22 Sodium carboxymethyl cellulose 0.1 to 0.3 Methyl cellulose 0.5 to 0.8 Water 40 to 50 the steps which comprise forming a substantially uniform solution in water of the sodium carboxymethyl cellulose, adding the methyl cellulose and agitating said mixture to effect the production of a substantially uniform admixture, adding water thereto, then adding the organic solubilizing agent and member selected from the group consisting of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains predominately from 8 to 18 carbon atoms, then adding the fatty acid alkanolamide in molten form and thoroughly admixing, then adding an aqueous solution of the polyphosphate, and then adding the lower alkanolamine in amounts essentially to form the alkanolamine salt of said member selected from the group consisting of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains from 8 to 18 carbon atoms.

3. In a method of making a heavy duty liquid detergent of the following composition in approximately the stated percentages by weight:

Member selected from the group consisting of diethanolarnine and triethanolamine salts of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains predominately from 12 to 15 carbon atoms 16 to 21 Sodium xylene sulfonate 6 to 9 Fatty acid alkanolamide in which the fatty acid radical contains predominately from 12 to 14 carbon atoms 3 to 4 Tetrapotassium pyrophosphate 18 to 20 Sodium carboxymethyl cellulose 0.15 to 0.2 Methyl cellulose u 0.6 to 0.7 Water 40 to 45 the steps which comprise forming a substantially uniform solution in water of the sodium carboxymethyl cellulose, methyl cellulose, sodium xylene sulfonate and the member selected from the group consisting of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains predominately from 12 to 15 carbon atoms, then adding the fatty acid alkanolamide in molten form and thoroughly admixing at a temperature of about 50 to 70 degrees C., then adding an aqueous solution of the tetrapotassium pyrophosphate, and then adding the member selected from the group consisting of diethanolamine and triethanolamine in amounts essentially to form the corresponding salt of said member selected from the group consisting of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains predominately from 12 to 15 carbon atoms.

4. In a method of making a heavy duty liquid detergent of the following Composition in approximately the stated percentages by weight:

Member selected from the group consisting of diethanolamine and triethanolamine salts of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains predomithe steps which comprise forming a substantially uniform solution in water of the sodium carboxymethyl cellulose, adding the methyl cellulose and agitating said mixture to effect the production of a substantially uniform admixture, adding water thereto, then adding the sodium xylene sulfonate and the member selected from the group consisting of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains predominately from 12 to 15 carbon atoms, then adding the fatty acid alkanolamide in molten form and thoroughly admixing at a temperature of about 50 to 70 degrees C., then adding an aqueous solution of the tetrapotassium pyrophosphate, and then adding the member selected from the group consisting of diethanolamine and triethanola-mine in amounts essentially to form the corresponding salt of said member selected from the group consisting of alkyl benzene and toluene sulfonic acids in which the alkyl radical contains predominately from 12 to 15 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,097,737 11/1933 Pickett et al. 25289 2,607,740 8/1952 Vitale et a1. 252l52 2,860,107 11/1958 Lamberti et al. 25289 2,920,045 1/1960 Hearn et a1 252137 2,943,058 6/1960 Cook 252153 2,994,665 8/1961 Reich et a1. 252137 3,075,922 1/1963 Wixon 252137 XR JULIUS GREENWALD, Primary Examiner.

ALBERT T. MEYERS, Examiner. 

1. IN A METHOD OF MAKING A HEAVY DUTY LIQUID DETERGENT OF THE FOLLOWING COMPOSITION IN APPROXIMATELY THE STATED PERCENTAGES BY WEIGHT: 